Molecular distillation process for the recovery of a ferulic acid ester of triterpene alcohol



United States Patent Ofiice 3,362,892 Patented Jan. 9, 1968 4 Claims. (ci. 203-89) ABSTRACT OF THE DISCLOSURE Method for producing concentrated Oryzanol by collecting a distillate in the range of 280 C. to 300 C. under a reduced pressure of mm. Hg to 10- mm. Hg abs. in the molecular distillation of dark oils of rice-bran.

Cross-reference Japanese Patent No. 227,801.

Brief description of invention This invention relates to a method for concentrating Oryzanol from dark oils of rice-bran by molecular distillation.

Detailed description of invention The words dark oils used throughout in this specification and claims means a dark oil of rice-bran or a product obtained by esterifying free fatty acids included in the dark oil of rice-bran with methyl alcohol or ethyl alcohol.

Oryzanol is a product obtained from rice-bran by extraction and purification and a mixture of ferulic acid (4-hydroxy-3 methoxy cinnamic acid) ester of triterpene alcohol.

It is a white or slightly yellowish powder having no odour or a slight odour and tasteless. It is readily soluble in chloroform, moderately soluble in acetone, ether or benzene and hardly soluble in water. Its absorbency li... e)

is 350-390 (0.05 g. of dried product, in 5000 ml. of isopropyl alcohol, at a 10 mm. layer).

It has been known as an active principle of pharmaceutical composition effective to automatic imbalance,

menopausal, middle aged and after castration. As for methods for producing Oryzanol concentrates, there has known a method disclosed in the Japanese Patent No. 227,801 which employs molecular distillation to produce Oryzanol from rice-bran oil or oil of embryo bud of rice. According to this method, Oryzanol is concentrated mostly in a distillate ranging from 200 C. to 230 C. in the falling-film type molecular distillation carried out under a reduced pressure in the range of 10 mm. Hg to 10'- mm. Hg.

An object of the present invention is to provide a method for producing an Oryzanol having a concentration higher than the one produced in the prior art method.

Such an object can be attained by the method of the present invention. It has now been found by the present inventors that when a dark oil of rice-bran or methyl ester of a dark oil of rice-bran is subjected to a molecular distillation under a reduced pressure of 10- mm. Hg to 10- mm. Hg by using a falling-film type molecular distillation apparatus, the Oryzanol is hardly concentrated in the distillate of 200 C. to 230 C., it is distilled rather at a temperature from 240 to 300 C. and is mostly concentrated in the distillate ranging from 280 C. to 300 C.

This tendency was confirmed both by a laboratory type falling film molecular distillation apparatus having an evaporation surface are-a of 240 cm.*, a distance between the evaporation surface and the condensation surface of 10 mm., and equipped with a heating system by a hot oil and an exhausting system consisting of a rotary pump having an exhausting velocity of 200 l./min. and a 4" oil diffusion pump having an exhausting velocity of 350 l./sec. at 10" mm. Hg and by a commercial falling film molecular distillation apparatus having an evaporation surface area of 0.58 m. a distance between the evaporation surface and the condensation surface of 30 mm. and equipped with a heating system by a vapor of hot heating medium oil and an exhausting system consisting of a rotary pump having an exhausting velocity of 3000 l./min., a 3" oil diffusion pump having an exhausting velocity of 1./sec. and an 8" oil diffusion pump having an exhausting velocity of 700 l./sec.

As for the diiference between a dark oil of rice-bran and methylester of the dark oil of rice-bran, there are slight differences in the distillation temperature and state but the distillation temperature of Oryzanol was the same in both the cases.

Following examples are specific illustrations of the present invention. All percents are by weight.

EXAMPLE 1 A methyl ester of dark oil of rice-bran was subjected to molecular distillation by the use of a commercial molecular distillation apparatus.

The results are summerized in Table 1.

TABLE 1.-MOLECULAR DISTILLATION OF METHYLESTER OF DARK OIL OF RICE-BRAN Distil- Percent 1% Vacuum degree lation Yield yiel E Content 0! Percent (mm. Ng) temper- (kg.) relative 1 cm. Oryzanol yield of ature to 011 (X315 my (percent) Oryzanol C.) n-heptane) Original Oil. 164. 0 100. 00 17. 2 4. 79 100.0 Fraction 1... 4-8X10. 101- 2 61. 0. 11 0.30 3. 87 Fraction 2.-. 4-5X10 240 4. 1 2. 50 13. 0 4. 17 2. 18 Fraction 3 The same as in the -260 6- 5 3. 97 31. 9 8. 88 7. 30

above fraction. Concentrated part according to the present invention:

Fraction 4 6. 0 3. 66 47. 2 13. 15 13.31 Fraction 5-. 16. 8 10. 25 53. 2 14. 31. 60 Fraction 6.- 16. 4 10.00 37. 4 10. 40 20. 90 Residue oil 13- 0 7. 93 46. 7 13. 00 21. 50

N 01E.Th8 contents of Oryzanol were calculated relative to the 11 1 cm. (A315 my, n-heptane) of 359.

3,362,892 3 4 EXAMPLE 2 2. A method according to claim 1 wherein a methyl A dark oil of rice-bran was subjected t molecular ester of dark oil of rice-bran is subjected to molecular distillation by the use of a laboratory type molecular distillationdistillation apparatus. The results are summarized in A m d aCC i g t Claim 1 wherein Said mol c- Table' 2. Mar distillation is of the falling film type.

TABLE 2.MOLEOULAR DISTILLATION OF DARK OIL OF RICE-BEAN Distil- Percent Content of Percent Vacuum degree lation No. of Yield yield Oryzanol yield (mm. Hg) tempercycle (g.) relative (percent) of ature C.) to oil Oryzanol Original oil 1, 834. 0 100.0 4. 62 Fraction 1. 1X10' -O 1 208. 0 11.3 0 Fraction The same as in the --180 1 759. 0 41. 4 0

above fraction. Fraction 3 .(10 2-20 1 236. 0 l2. 8 0.30 0.83 Fraction 4 5 lO- -230 1 26. 8 l. 46 3.1 0. 98 Fraction 5 The same as in the 240 1 29. 2 1.59 4. 5 1. 65

above fraction. Fraction 6 1 31. 7 1. 73 7. l 2. 66 Fraction 7. -2li0 l 44. 5 2. 42 12. 0 6. 44 Fraction 8 270 1 45. 5 2. 48 18. 0 9. 67 Concentrated par according to the present invention:

Fraction 9 The same as in the 280 1 42. 7 2. 33 24. 0 12.10

above fraction. Fraction l0 290 1 50. 0 2. 72 24. 3 14. 40 Fraction 11..- -300 2 81. 8 4. 46 20. 0 19, 40 Fraction l2 3(l0 4 144. 9 7. 88 11. 0 18. 17 Residual oil 85. 2 4. 9. 0 9.06

Nora-The contents of Oryzanol were calculated relative to the E i (R315 my, n-heptane) of 359.

What 1s claimed 15: 4. A method accordrng to claim 2 wherein said molec- 1. A method of recovering a ferulic acid ester of ular distillation is of the falling film type. triterpene alcohol comprising subjecting dark oil of ricebran containing a ferulic acid ester to molecular distil- No Tefermces cltedl-ation, and collecting a distillate in the range of 280 C. to 300 C. under reduced pressure Within the range of 35 WHBUR BASCOMB Pmnary Examiner 10- mm. Hg to 10- mm. Hg. P. E. DRUMMOND, Assistant Examiner. 

